Hindered Rotation in Some Organic Dithiocarbamates

Abstract

Hindered rotation in alkyldithiocarbamates of the type RR′NC(= S)SR″ [R, R′, R″ = Me, Me, Et (1); PhCH₂, Me, Et (2); PhCH₂, H, Et (3); PhCH₂, H, Me (4) and O(CH₂CH₂)₂, Et (5)′ has been investigated using variable-temperature ¹H NMR spectroscopy in CDCl₃, C₆D₆, and DMSO-d₆ solutions. Rotational parameters were calculated by the coalescence temperature method. Nitrogen substituent effects on the free energy of activation and on the equilibrium constant of unsymmetrical conformers at room temperature are discussed.     

Direct Evidence for Intermolecular Oxidative Addition of σ(Si?Si) Bonds to Gold

Oxidative addition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl₃, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative ³¹P and ²⁹Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si Si) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations.     

The influence of porosity of ammonium perchlorate (AP) on the thermomechanical and thermal properties of the AP/polyvinylchloride (PVC) composite propellants

The influence of porous ammonium perchlorate (P_OAP) on the thermomechanical and combustion behavior of solid rocket propellants based on polyvinylchloride binder has been investigated. Differential scanning calorimetry, differential thermogravimetry, dynamic mechanical thermal analysis, and scanning electronic microscopy measurements were used for thermomechanical and thermal decomposition properties assessment. The results obtained indicate that lower glass transitions of the propellants and catalytic effect of combustion are obtained with P_OAP.     

An SFG and DFG investigation of Au(111), Au(100), Au(110) and Au(210) electrodes in contact with aqueous solutions containing KCN

In this paper, the behaviour of Au(111), (100), (110) and (210) electrodes in contact with pH-neutral aqueous solutions of KCN has been studied as a function of potential by means of in situ sum frequency generation (SFG) and difference frequency generation (DFG) spectroscopies. The contribution of both free and bound electrons has been included. Spectroelectrochemical results were complemented with cyclic voltammetric measurements. The main emphasis in this work has been placed on systematising and quantifying the interaction between the vibrational and electronic structures of the electrodic interfaces studied by the systematic comparison of SFG and DFG spectra measured under the same electrochemical conditions for different crystal orientations.     

Non-overlapping Domain Decomposition Method for a Nodal Finite Element Method

A new approach is proposed for constructing nonoverlapping domain decomposition procedures for solving a linear system related to a nodal finite element method. It applies to problems involving either positive semi-definite or complex indefinite local matrices. The main feature of the method is to preserve the continuity requirements on the unknowns and the finite element equations at the nodes shared by more than two subdomains and to suitably augment the local matrices. We prove that the corresponding algorithm can be seen as a converging iterative method for solving the finite element system and that it cannot break down. Each iteration is obtained by solving uncoupled local finite element systems posed in each subdomain and, in contrast to a strict domain decomposition method, is completed by solving a linear system whose unknowns are the degrees of freedom attached to the above special nodes.     

In situ electrochemical SFG/DFG study of CN⁻ and nitrile adsorption at au from 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ionic liquid([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]diazenyl} benzonitrile (CTDB) and K[Au(CN)₂

In this paper we report an in situ electrochemical Sum-/Difference Frequency Generation (SFG/DFG) spectroscopy investigation of the adsorption of nitrile and CN? from the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]-diazenyl}benzonitrile (CTDB) at Au electrodes in the absence and in the presence of the Au-electrodeposition process from K[Au(CN)?]. The adsorption of nitrile and its coadsorption with CN? resulting either from the cathodic decomposition of the dye or from ligand release from the Au(I) cyanocomplex yield potential-dependent single or double SFG bands in the range 2,125-2,140 cm?1, exhibiting Stark tuning values of ca. 3 and 1 cm?1 V?1 in the absence and presence of electrodeposition, respectively. The low Stark tuning found during electrodeposition correlates with the cathodic inhibiting effect of CTDB, giving rise to its levelling properties. The essential insensitivity of the other DFG parameters to the electrodeposition process is due to the growth of smooth Au.